Stereoregular polymer and monomer thereof and process for production of both

ABSTRACT

An ester derivant having a crystal structure in which the molecules in two adjacent molecule planes are antiparallel is created from a carboxylic acid having carbon-carbon double bond and a compound having a functional group that can react to a carboxyl group of the carboxylic acid. The crystal of the ester derivant is then subjected to light irradiation or heating.

TECHNICAL FIELD

The present invention relates to a stereoregular polymer and monomerthereof, and process for production of both.

BACKGROUND ART

Physicalities of polymer depend on the primary structure of the polymerchain. Therefore, in the composition of polymer, the reaction structureis designed by controlling the primary structure, such as molecular massof polymer, molecular mass distribution, terminal structure, branchstructure, or stereo structure. In recent years, in addition to such aminute control of the primary structure of polymer chain, there has beena trend of controlling the higher-order structure, such asstereoregularity of polymer compound by controlling assembly of polymerchain, such as grouping, self-assembly, crystallization, or phaseseparation.

As an example of the control of higher-order structure, there is amethod of using crystal lattice with a specific molecular sequence ofthe reaction field for polymerization reaction. More specifically, whenusing a monomer molecule in crystallization state, since the monomermolecule itself has a reaction field of the polymerization reaction, astereoregular polymer can be produced by proceeding polymerizationreaction, with minimum movement of atoms or substituent, withoutchanging position of center of gravity of each monomer molecule, orsymmetry of the crystal in polymerization reaction. Such polymerizationreaction is called topochemical polymerization.

The reaction path and reaction speed of topochemical polymerizationdepend on the crystal structure, that is an aggregation of monomermolecules, and the structure of the resultant polymer is determineddepending on the molecular sequence of the crystal. Further, producing apolymer through the topochemical polymerization makes it possible toobtain a polymer without separation or purification, and also, since theprocess may be done without an organic solvent, it causes lessenvironmental burden.

The foregoing method of proceeding the topochemical polymerization underthe control of crystal lattice allows easy production of a stereoregularpolymer. With this finding, there have been active studies of thetopochemical polymerization with the reports about solid-phasepolymerization of diacetylene (Document: H. Basser, Adv. Polym. Sci.,63, p. 1 (1984) etc.), and solid-phase polymerization of olefin(Document: M. Hasegawa, Adv. Phys. Org. Chem., 30, p. 117 (1995) etc.)etc. Further, the inventors of the present invention have reportedtopochemical polymerization of diene monomer (Document: A. Matsumoto, T.Matsumura, S. Aoki, J. Chem. Soc., Chem. Commun., 1994, p. 1389).

The topochemical polymerization of diene monomer is explained below withan example, (Z, Z)-1,4-butadiene (hereinafter referred to as dienemonomer) having substituents Y₁ and Y₂, shown in FIGS. 11 and 12. Notethat, the substituents Y₁ and Y₂ are identical in this example.

As shown before the arrow of FIG. 11, the diene monomer has a crystalstructure in which all the monomer molecules are aligned in the samedirection in a column. More specifically, when viewing the plane(molecular plane) having the monomer molecules from one side of thelamination direction (column direction), all the monomer molecules inthe molecular plane face the same direction. In other words, if assumingthe molecule plane from one side of the lamination direction is theupper surface, all the molecular planes formed by the monomer moleculesare stacked showing upper surfaces.

Therefore, when topochemical polymerization occurs in the diene monomer,the diene monomers of FIG. 11 are bonded together at the positionsdenoted by the broken line, thus producing a polymer. As shown in FIG.11, the produced polymer (diene polymer) has repeating units:—CHY₁—CH═CH—CHY₂—. The repeating units of each diene polymer have thesame configuration in the vicinity of the carbons to which thesubstituents Y1 and Y2 are bonded. The polymer having thisstereoregularity is called a diisotactic.

On the other hand, there exists an isomer of the diisotacticstereoregular polymer, having disyndiotactic structure. As mentionedabove, the physicalities of polymer depend on the stereoregularity.Therefore, the polymer having the stereoregularity of disyndiotacticdiffers in crystallization, mechanical characteristic, solventresistance, thermostability etc. from the diisotactic polymer.

As shown after the arrow in FIG. 12, the disyndiotactic structurepolymer has such a stereoregularity that the repeating units of—CHY1-CH═CH—CHY2-in the vicinity of the carbons to which thesubstituents Y1 and Y2 are bonded are alternately identical. Morespecifically, in the disyndiotactic polymer, the two adjacent units havedifferent configurations in the vicinity of the carbons to which thesubstituents Y1 and Y2 are connected. In other words, the disyndiotacticpolymer has repeating units in which two kinds of units with differentconfigurations alternately appear with a certain cycle.

To obtain such a disyndiotactic polymer through topochemicalpolymerization, as shown before the arrow of FIG. 12, there has been atechnique of stacking the molecular planes so that the upper surface andthe rear surface alternately appear (Document: A. Matsumoto, S.Nagahama, T. Odani, J. Am. Chem. Soc., 122, p. 9109 (2000); A.Matsumoto, Prog. React. Kinet. Mecha., 26, p. 59 (2001) etc). Morespecifically, when viewing the planes (molecular plane) having themonomer molecules from one side of the lamination direction, thedirection of the monomer molecules in the molecular plane is alternatelyidentical. Further, by causing topochemical polymerization in themonomer molecules having such a crystal structure, a diene monomer isproduced at the position denoted by the broken line in the figure.Further, it is assumed that a disyndiotactic polymer is also obtained,as shown after the arrow in FIG. 12.

However, there has been no report of actual acquirement ofdisyndiotactic polymer through the topochemical polymerization. Morespecifically, in prior art, there has been a proposal of obtaining adisyndiotactic polymer by using the monomer molecules having thestructure shown in FIG. 12, but there is no report of successfulacquirement of disyndiotactic polymer by using the diene monomermolecules shown in FIG. 12, or through topochemical polymerization ofthe diene monomer molecules.

The present invention is made in view of the foregoing conventionalproblems, and an object is to find the diene monomer having thestructure of FIG. 12, and to provide a stereoregular polymer withdisyndiotactic characteristic through polymerization of the dienemonomer. The present invention further provides the manufacturingmethods thereof.

DISCLOSURE OF INVENTION

In order to solve the foregoing problems, s stereoregular polymer of thepresent invention has a disyndiotactic structure with hydrocarbon chainrepeating units each having at least one ester substituent.

The stereoregular polymer has such a structure that an atom(stereocenter hereinafter), constituting the main-chain and having afunctional group such as an ester substituent, has a regularconfiguration. The regularity of the stereoregular polymer isdisyndiotactic. In the disyndiotactic structure, the configurations ofthe stereocenters are not all identical but alternately identical in therepeating units. More specifically, in the disyndiotactic structure, thestereocenters of the adjacent repeating units have differentconfigurations, and those adjacent units with different configurationsconstitute a unit in the iteration.

Examples of the stereoregular polymer of the present invention include avinyl including repeating units of chain hydrocarbon having single bondbetween carbons, or a dien polymer containing double bond betweencarbons. Among these, a particularly preferred is a dien stereoregularpolymer having a carbon-carbon double bond in the repeating units.

Further, the main chain of the repeating unit preferably has at leasttwo substituents. The substituents may be both ester substituents oronly one of them is an ester substituent. The unit may contain othersubstituents as long as it has at least one ester substituent.Accordingly, the monomer of the vinyl polymer is preferably a 1,2-disubstitution product (α, δ-disubstitution product), and the monomer ofthe dien polymer is preferably a 1,4-di substitution product (α,δ-disubstitution product). Further, it may also be a derivant of thedisubstituent or a multi-substitution product having more substituentsin addition to these disubstituents.

The ester substituent is not particularly limited. For example, it maybe an aster substituent with a function group of hydrocarbon group,halogenated hydrocarbon, amino group, or an aminoalkyl group. A mostpreferred is an ester substituent having a benzyl group containing etherbond.

Note that, the hydrocarbon group as a functional group is not limited,and may be either a saturated hydrocarbon group, or an unsaturatedhydrocarbon group, and either a chain hydrocarbon group or a cyclichydrocarbon group.

Specifically, the stereoregular polymer preferably has repeating unitsdenoted by a general formula (1):

where R₁ and R₂ are hydrocarbon groups, each of which may have afunctional group.

The functional group refers to a functional group other than thehydrocarbon group. The R₁ and R₂ are only required to be a hydrocarbongroup having a functional group other than a hydrocarbon group. Apreferred example is a benzyl group containing ether bond. Particularlyreferable examples for the ether bond in the benzyl group areCH₃O—(methoxy group), C₂H₅O—(ethoxy group), C₃H₇O—(propoxy group),C₄H₉O—(butoxy group), C₆H₅O—(phenoxy group).

Further, in the stereoregular polymer denoted by the general formula (1)above, the configuration at the carbon-carbon double bond preferably hasa trans-configuration.

With this structure, the stereoregular polymer of the present invention,whose stereoregularity is disyndiotactic, is superior in crysterization,mechanical characteristic, solvent resistance thermostability than thepolymer with diisotactic structure. Here, the polymer with diisotacticstructure has repeating units having stereocenters with the sameconfigurations.

More specifically, when used singly or as a polymer alloy combined withan existing polymer, the stereoregular polymer of the present inventionbecomes superior in thermostability, flame resistance, elasticity,pulling strength, flexural strength, shock-resistance, abrasionresistance, linear expansivity, dimensional stability, moldability,electric property, dielectric breakdown strength, permittivity,high-temperature property, antiweatherbility, or antihydrolytic.

The existing polymer to be combined with the stereoregular polymer ofthe present invention to create a polymer alloy may be a general-purposepolymer, a condensed polymer, an engineering plastic, a super engineerplastic or the like. For example, the general-purpose polymer may bepolyolefine, dien polymer, vinyl polymer; and the condensed polymer maybe polyester, polyamide, polyurethane etc. Further, engineering plasticor a super engineering plastic may be nylon, polyacetal, polycarbonate,denatured polyphenyleneoxide, polybutyleneterephthalate,polyethyleneterephthalate, polyphenylene sulfide, polysulfone,polyarylete, polyetherketone, polyimide etc.

The complexation to create polymer alloy may be performed throughblending, IPN (Inter Penetrating Polymer Network), block grafting etc.Further, an inorganic material such as a glass fiber, carbon fiber maybe mixed.

Therefore, the stereoregular polymer of the present invention may beused for electric, electronic material, injection molding circuitsubstrate, OA device component, magnetic disk, car outer panel,fuel-related component, electric-equipment-related component, carexterior equipment, car inner equipment, aircraft component, sportequipment, building material exterior, agricultural material, sundrygoods, food wrapping etc.

Further, an ester derivant of the present invention has a carbon-carbondouble bond and has a lamination crystal structure wherein molecules intwo adjacent molecule planes are antiparallel.

The molecular plane refers to a plane formed by a carbon-carbon doublebond of the molecules of the ester derivant. Further, to explain morespecifically the structure in which molecules in two adjacent moleculeplanes are antiparallel, two adjacent molecular planes in the crystalstructure of the ester derivant are oppositely stacked. That is, the oneof two molecular planes adjacent in the lamination direction is theupper surface and the other is the rear surface when viewing from oneside of the lamination direction.

The ester derivant is only required to be an ester derivant having acarbon-carbon double bond, but is preferably a dien containing an estersubstituent, and more preferably a conjugate dien containing an estersubstituent.

Further, it is preferable that ester derivant has at least twosubstituents, one of which is an ester substituent. The estersubstituent is not particularly limited, and a suitable example may beone having a functional group of a hydrocarbon group, halogenatedhydrocarbon group, amino group, or aminoalkyl group.

The conjugate dien having an ester substituent, one of an example ofester derivant, may be a muconic acid derivant or a sorbic acidderivant, for example.

More specifically, the ester derivant is preferably denoted by a generalformula (2):R₃OOC—CH═CH—CH═CH—COOR₄   (2)

where R₃ and R₄ are hydrocarbon groups, each of which may have afunctional group.

The R₃ and R₄ are only required to be a hydrocarbon group having afunctional group other than a hydrocarbon group. A preferred example isa benzyl group containing ether bond. Particularly referable examplesfor the ether bond in the benzyl group are CH₃O—, C₂H₅O—, C₃H₇O—, C₄H₉O—, C₆H₅O—.

The ester derivant denoted by the foregoing general formula (2)preferably has a constant configuration at the portion of carbon-carbondouble bond. Namely, the ester derivant of the general formula (2) ispreferably a (Z, Z) form, or a (E, E) form. However, (E, Z) form mayalso be used.

In the foregoing structure, as described above, the ester derivant ofthe present invention forms a crystal in which the molecules alternatelyface upward or downward. Therefore, as described later, by proceedingpolymerization reaction in such a crystal structure, a stereoregularpolymer of disyndiotactic structure may be obtained. That is, the esterderivant is useful to create the stereoregular polymer.

Further, a production method of an ester derivant of the presentinvention comprises the step of forming a lamination crystal structureusing a carboxylic acid having a carbon-carbon double bond and acompound having a functional group that can react to a carboxyl group ofthe carboxylic acid, so that molecules in two adjacent molecule planesare antiparallel.

The carboxylic acid is only required to be one having a carbon-carbondouble bond; preferable example include a single base unsaturatedcarboxylic acid, such as sorbic acid, crotonic acid, or tiglic acid; anda dibasic unsaturated carboxylic acid, such as muconic acid, maleicacid, fumaric acid, citraconic acid, or mesaconic acid. A preferred is amuconic acid or a sorbic acid containing conjugate dien.

Further, the compound containing a functional group reacting to thecarboxyl group is not limited, and is only required to be one allowingthe hydrocarbon group having a functional group other than a hydrocarbongroup to be incorporated in the carboxylic acid having dien. A possibleexample may be halogenated benzyl containing ether bond.

With this method, obtained is an ester derivant having a crystalstructure in which the molecules in the adjacent molecular planes areantiparallel. Therefore, as described later, by proceedingpolymerization reaction in such a crystal structure, a stereoregularpolymer of disyndiotactic structure may be obtained.

Note that, the esterification in the foregoing method is not limited,and one of the conventional methods may be used; a possible example maybe esterification with heating/dehydration in the presence of acidcatalyst, or esterification with reaction of acid chloride and alcohol.

Further, apart from the conventional esterification, the foregoingprocess may be performed by reacting a carboxylic acid having acarbon-carbon double bond with a compound having a functional group thatcan react to a carboxyl group of the carboxylic acid dien, usinghexamethylphospholamide as a solvent, in the presence of a potassiumcarbonate.

Particularly, by carrying out esterification with a solvent ofhexamethylphospholamide and a catalyst of potassium carbonate, an esterderivant with specific stereoregularity can be obtained at a higher ratewhile suppressing isomerization of the product. Namely, the foregoingesterification carries out reaction with secure acquirement of an esterderivant having a specific configuration at a high selectivity.

Note that, the foregoing esterification method is not limited to themethod of producing an ester derivant with a column structure in whichthe molecules of two adjacent molecular planes are aligned inantiparallel, like the one according to the present invention. Themethod will be suitably used for esterification of various carboxylicacid diens. Namely, the foregoing esterification method suppresses theisomerization in esterification reaction as much as possible, allowinghigh-rate acquirement.

Further, a production method of a stereoregular polymer of the presentinvention comprises the step of polymerizing a crystal of the esterderivant containing dien either by light irradiation or heating of thecrystal.

This method carries out polymerization either by irradiation or byheating, while maintaining the ester derivant in a crystal state.Polymerization reaction in a crystal state ensures strong binding ofmolecule alignment in the crystal. Therefore, as with the ester derivantof the present invention, when the polymerization is performed to acrystal in which molecules in two adjacent molecule planes areantiparallel, it is possible to proceed polymerization reaction with aspecific stereoregularity. Namely, by using an ester derivant having acontrolled crystal structure formed by molecules, it is possible toobtain a stereoregular polymer of a disyndiotactic structure.

Note that, the light irradiation may be performed by visible light,ultraviolet light, X-ray or γ-ray; and ultraviolet light, X-ray or γ-rayare particularly preferable. With X-ray or γ-ray with high-permeability,reaction evenly occurs in the entire of the crystal, thus obtaining acrystal of a stereoregular polymer with significantly reduceddeformation or defect.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a drawing illustrating structures of a stereoregular polymerof the present invention and the monomer thereof.

FIGS. 2(a) through 2(c) are drawings illustrating the structure of (Z,Z)—muconic acid di(4-methoxy benzyl) found by X-ray crystal structureanalysis.

FIGS. 3(a) and 3(b) are drawings illustrating X-ray crystal structureanalysis of (Z, Z)—muconic acid di(4-methoxy benzyl).

FIG. 4 is a drawing showing a lamination of (Z, Z)—muconic aciddi(4-methoxy benzyl).

FIGS. 5(a) and 5(b) are drawings illustrating X-ray crystal structureanalysis of (E, E)—muconic acid di(4-methoxy benzyl).

FIG. 6 is a drawing showing a lamination of (E, E)—muconic aciddi(4-methoxy benzyl).

FIG. 7 shows infrared absorption spectrum of polymuconic aciddi(4-methoxy benzyl) obtained by the (Z, Z)—muconic acid di(4-methoxybenzyl) and (E, E)—muconic acid di(4-methoxy benzyl).

FIG. 8 shows powder X-ray diffraction spectrum of polymuconic aciddi(4-methoxy benzyl) obtained by the (Z, Z)—muconic acid di(4-methoxybenzyl) and (E, E)—muconic acid di(4-methoxy benzyl).

FIG. 9(a) and 9(b) are drawings illustrating X-ray crystal structureanalysis of (Z, Z)—polymuconic acid di(4-methoxy benzyl).

FIG. 10 shows powder X-ray diffraction spectrum of polymuconic acidobtained by the (E, Z)—muconic acid (4-methoxy benzyl) and polymuconicacid (4-methoxy benzyl) obtained therefrom.

FIG. 11 is a conceptual diagram illustrating structures of astereoregular polymer of a diisotactic structure and the monomerthereof.

FIG. 12 is a conceptual diagram illustrating structures of astereoregular polymer of a disyndiotactic structure and the monomerthereof.

BEST MODE FOR CARRYING OUT THE INVENTION

One embodiment of the present invention is described below withreference to FIGS. 1 and 2.

A. Structures of Stereoregular Polymer and the Monomer thereof

With reference to FIGS. 1 and 2, the following describes the structureof stereoregular polymer, and the structure of monomer constituting thestereoregular polymer, an ester derivant.

1) Structure of Stereoregular Polymer

The stereoregular polymer of the present invention, whosestereoregularity is disyndiotactic, contains at least one estersubstituent.

The repeating units of the stereoregular polymer is preferably formed bysubjecting muconic acid derivant to polymerization; that is, it ispreferable that the repeating unit is one denoted by the foregoinggeneral formula (1). Further, R₁ and R₂ of the general formula (1)express hydrocarbon groups, each of which may have a functional group,and are preferably a benzyl group having ether bond.

That is, the stereoregular polymer of the present invention ispreferably has repeating units denoted by the following general formula(3),

where R₅ expresses a benzyl group having ether bond, and R₆ expresses ahydrocarbon group. Further, it is more preferable that R₆ is a methylgroup, that makes R₅ a methoxy benzyl group.

The following example uses the stereoregular polymer (hereinafterreferred to as a muconic acid polymer) having the repeating unitsdenoted by the general formula (3).

As shown after the arrow in FIG. 1, the stereoregularity of this muconicacid polymer is disyndiotactic. Specifically, in this muconic acidpolymer, the configuration of two carbons (hereinafter referred to as astereocenter) to which —COOR₅ are bonded in the repeating unit differsfrom that of the two stereocenters in an adjacent unit. Theconfigurations of the stereocenters of the respective repeating unitsare alternately identical.

In other words, the muconic acid polymer has repeating units eachdenoted by the general formula (3), but there are two kinds of repeatingunit with different configurations of stereocenter. These differentunits alternately appear with a certain cycle. Such a stereoregularityis called disyndiotactic.

1) Structure of Monomer

Next, the following explains a monomer (muconic acid monomerhereinafter) used to obtain the muconic acid polymer. As describedabove, the muconic acid polymer denoted by the general formula (3) isformed through polymerization of a muconic acid derivant. Therefore, themuconic acid monomer is preferably expressed by the following generalformula (4),R₅OOC—CH═CH—CH═CH—COOR₅   (4)

where R₅ expresses a benzyl group having ether bond.

The substituent (—COOR₅) contained in the muconic acid monomer denotedby the foregoing formula (4) is identical to the substituent containedin the muconic acid polymer denoted by the foregoing formula (3).

As shown before the arrow in FIG. 1, each muconic acid monomer of thegeneral formula (4) has a molecular plane having a carbon-carbon doublebond. The muconic acid monomer may be a (Z, Z) form in which both of theconfigurations of the carbon-carbon double bond are cis-constitution, a(E, E) form in which both of the configurations of the carbon-carbondouble bond are trans-constitution, or a (E, Z) monomer in which one ofthe configurations of the carbon-carbon double bond is cis and the otheris trans-constitution. Among these three isomers, the (Z, Z) form or the(E, E) form is preferred to obtain the muconic acid polymer. The use of(E, Z) polymer however still allows acquirement of the foregoing muconicacid polyrmer.

As shown in FIG. 1, a muconic acid monomer of the (Z, Z) form or the (E,E) form has a crystal of column structure in which the molecular planesare laminated. In this structure of crystal, the one of two molecularplanes adjacent in the lamination direction is the upper surface and theother is the rear surface when viewing from one side of the laminationdirection. Namely, the crystal of muconic acid monomer has a columnstructure in which the upper and rear molecular surfaces alternatelyappear in the lamination. In other words, the crystal of muconic acidmonomer has a column structure in which the molecules are aligned sothat the molecules in the two adjacent molecule planes are antiparallel.The crystal of the muconic acid monomer contains plural columnstructures that are aligned in the direction vertical to the laminationdirection.

The reason why the crystal of muconic acid monomer has such a columnstructure may be thus assumed: there is weak intermolecular interactionbetween the adjacent muconic acid monomers within the column structureand between the column structures.

As a general sense, the molecular alignment of the crystal of monomer isgreatly changed in the presence of strong intermolecular interaction,such as hydrogen bond or ionic bond. That is, a monomer forms a crystalby cooperation of the specific-hydrogen-bond orientation and thespecific-ionic-bond intermolecular interaction.

Meanwhile, there is a theory that relatively weak intermolecularinteraction than the hydrogen bond or ionic bond also functions as afactor for controlling the molecular alignment of the crystal. Examplesof the weak intermolecular interaction include halogen-halogeninteraction, π-π stacking, CH/O interaction, CH/N interaction, CH/πinteraction, or the like. The halogen-halogen interaction is said to becaused by the anisotropy of the electron distribution on the halogenatom, and the π-π stacking is interaction among π electrons that iscaused when the π planes of two aromatic rings are oppositely aligned.The CH/O interaction, and the CH/N interaction occur when the OH or NH,that relates to strong hydrogen bond such as OH/O or NH/H, is replacedwith CH weaker in degree of acidity. Further, CH/π interaction occurswhen the OH or N is replaced with a π electron weaker in basicity.

The inventors of the present invention have reported that the crystal ofthe monomer formed by the strong hydrogen bond, such as OH/O or NH/H, orby intermolecular force using halogen-halogen interaction tends to forma column structure in which the molecules are aligned in parallel.

On the other hand, the crystal of the muconic acid monomer is assumed tobe formed by relatively weak intermolecular interaction, such as theCH/O interaction, the NH/N interaction, or the CH/π interaction, thatoccurs within the column structure and between the column structures.Therefore, in the crystal of the monomer formed by such a weakintermolecular interaction, such as the crystal of muconic acid monomerof the present invention, tends to have a column structure in which themolecules are aligned in antiparallel.

With reference to FIGS. 2(a) through 2(c), the following describes anexample using the muconic acid monomer of the general formula (4) inwhich R₅ is a methoxy benzyl group.

In the column structure of the muconic acid monomer, it is assumed thatthe CH/O interaction and the CH/π interaction occur between the monomersadjacent in the column direction. As denoted by the broken line in 2(b),the CH/O interaction occurs between the hydrogen at the portion of thecarbon-carbon double bond and the carbonyl oxygen of the carboxyl group.Further, as denoted by the chain double-dashed line in FIGS. 2(a) and2(c), the CH/π interaction occurs between the methoxy group of themethoxy benzyl group and the benzene ring. In contrast, in the columnstructure, as shown in FIG. 2(b), the CH/O interaction occurs betweenthe methoxy groups of the methoxy benzyl groups contained in themonomers adjacent in the direction vertical to the column direction.

As explained, the molecular alignment of the crystal of muconic acidmonomer is controlled by the CH/O interaction and the CH/π interactionthat occur within the column structure and between the columnstructures. Therefore, the crystal of muconic acid polymer has astructure in which the molecules in the two adjacent molecule planes arealigned in antiparallel in the column structure, while the columnstructure is aligned in the direction orthogonal to the laminationdirection.

B. Production Methods of Stereoregular Polymer and the Monomer thereof

The following describes production methods of stereoregular polymer andthe monomer thereof. Note that, as with the example above, the followingexample also uses the muconic acid polymer denoted by the foregoinggeneral formula (3) as a stereoregular polymer, and the muconic acidmonomer denoted by the foregoing general formula (4) as the monomer, andthe respective production methods are described.

1) Production Method of Muconic Acid Polymer

The muconic acid polymer with the configuration explained in the A 1)above may be obtained through solid-phase polymerization, that clearlyshows steleoselectivity and stereospecificity, allowing control of thestructure of the product. Specifically, the muconic acid polymer may beobtained by subjecting the muconic acid monomer described in A 2) aboveto solid-phase polymerization.

Topochemical polymerization is preferably performed as the solid-phasepolymerization. In the topochemical polymerization, a stereoregularpolymer can be produced by proceeding polymerization reaction, withminimum movement of atoms or substituent without changing position ofcenter of gravity of each monomer molecule, or symmetry of the crystalin polymerization reaction. The reaction path and reaction speed intopochemical polymerization depend on the crystal structure, that is anaggregation of monomer molecules, and the structure of the resultantpolymer is determined depending on the molecular sequence of thecrystal. Therefore, the topochemical polymerization allows acquirementof a polymer with desired structure by control of crystal structure ofthe monomer, thereby easily producing a polymer having specific stereoregularity.

More specifically, topochemical polymerization is caused in the muconicacid monomer (shown before the arrow in FIG. 1) having a crystal of acolumn structure by performing light irradiation using visible light,ultraviolet light, X-ray, γ-ray etc. or by heating the monomer. Throughthis polymerization, obtained is a muconic acid polymer. In other words,the muconic acid monomers are bonded at the position denoted by thebroken lines shown in FIG. 1 through topochemical polymerization, thusproducing a muconic acid polymer.

In topochemical polymerization with light irradiation, the lightirradiation is preferably performed at room temperature for a time rangefrom 10 minutes to 100 hours, more preferably for 1 hour to 10 hours. Onthe other hand, in topochemical polymerization by heating, the heatingis preferably performed at 40° C. to 200° C., more preferably at 80° C.to 120° C. Further, the heating time may be decided according to heatingtemperature, but preferably in a range from 10 minutes to 200 hours,more preferably 1 hour to 20 hours. Further, the topochemicalpolymerization may be performed with both light irradiation and heating,so that the polymerization time is reduced.

Note that, to obtain the foregoing muconic acid polymer, it ispreferable to use the crystal of (Z, Z) form or that of (E, E) form.

As explained, in topochemical polymerization, polymerization reaction iscaused in a solid body by light irradiation or heating; therefore, otheradditives than monomer, such as reaction solvent, catalyst etc. is notrequired, and separation of the produced polymer is not necessary.Further, since all the monomer materials can be converted into polymers,it produces no wastes, thus reducing environmental burden.

2) Production Method of Muconic Acid Monomer

The muconic acid monomer explained in the A 2) above may be obtained byreacting of muconic acid and halogenide of methoxy benzyl so as toesterify the carboxyl group of muconic acid. A synthetic muconic acidmonomer may be made of a (Z, Z) form muconic acid and a (E, E) formmuconic acid. Since the (E, E) form of muconic acid is morethermodynamically stable then the (Z, Z) form muconic acid, the (Z, Z)form muconic acid is more preferable for the starting material.

The (Z, Z) form muconic acid, as the starting material, is reacted withhalogenide of methoxy benzyl in the presence of potassium carbonate,using a hexamethylphosholamide (HMPA) as a solvent, thus producing amuconic acid monomer as a mixture of (Z, Z) form muconic acid and (E, Z)form muconic acid (Formula 5).

(R7 expresses methoxy benzyl group, and X′ expresses halogen)

The (Z, Z) form and (E, Z) form are generally dividable by columnchromatography. Thus, the (Z, Z) form muconic acid monomer and the (E,Z) form muconic acid monomer produced through the reaction of formula(5) can be obtained as separated monomers.

Further, a (E, E) form muconic acid monomer may be obtained by thereaction of the formula (5) as in the example above, that produces amuconic acid monomer as a mixture of (Z, Z) form and (E, Z) form. Then,by irradiating the (Z, Z) form muconic acid monomer and the (E, Z) formmuconic acid monomer with ultraviolet light or other light, they areisomerized into the (E, E) form muconic acid monomer that is morethermodynamically stable. In this way, only a (E, E) form muconic acidmonomer is obtained.

The amount of muconic acid and halogenide of methoxy benzyl used for theforegoing esterification reaction may be decided so that their amountsare equal in theoretical quantity. More specifically, it should bedecided so that the number of the carboxyl group of the muconic acid andthe methoxy benzyl group contained in the halogenide of the methoxybenzyl are equal. The amount of hexamethylphosholamide is not limitedbut should be enough to dissolve the muconic acid. Further, thepotassium carbonate is preferably 0.5 to 10 times, more preferably 1 to2 times the muconic acid in theoretical amount.

The foregoing method does not produce a mixture of (E, Z) form and (E,E) form, that is not easily separated by column chromatography;therefore, the method produces highly purified (Z, Z) form, (E, Z) formand (E, E) form. Further, if the method is performed with the sameesterification as the formula (5), it is possible to obtain the (Z, Z)form muconic acid monomer as the main product.

The foregoing new method of esterificating carboxylic acid has beenfound by the inventors of the present invention. This esterificationmethod differs from those conventionally performed, for example,esterification with heating/dehydration in the presence of acidcatalyst, or esterification with reaction of acid chloride and alcohol.

In the foregoing conventional method, particularly in esterificatingcarboxylic acid diene; an esterification compound, the product of thereaction, is included in the isomer, that is a mixture of (Z, Z) form,(E, Z) form and (E, E) form, depending on the material and the reactioncondition. However, in the foregoing conventional method, isomerizationto the (E, Z) form and (E, E) form more easily occurs, and there is somedifficulties to obtain (Z, Z) form at a high rate. Further, separationof (E, Z) form to/from (E, E) form is considered more difficult;therefore the resulting isomers are not obtained as separate monomers.

In contrast, as described above, with the use of a solvent ofhexamethylphospholamide and a catalyst of potassium carbonate,esterification compound of (Z, Z) form can be obtained at a higher ratewhile suppressing isomerization into (E, Z) form or (E, E) form.Further, the resulting esterification compounds do not include a mixtureof (E, Z) form and (E, E) form, thus easily obtaining the respectiveisomers. Namely, the esterification method of the present inventionsuppresses the isomerization as much as possible, allowing acquirementof esterification compound, thus obtaining an esterification compoundwith a specific configuration at a high rate.

Note that, the foregoing esterification method is not limited to theexample described in the A 2) above, that produces a muconic acidmonomer with a column structure in which the molecules of two adjacentmolecular planes are aligned in antiparallel. As described later inExamples, the method will be suitably used for obtaining variousesterification compounds. Namely, the foregoing esterification methodcan be widely used as a method of suppressing the isomerization inesterification reaction as much as possible, allowing high-rateacquirement of an esterification compound with a specific configuration.

The concrete Examples of the present invention are described below withreference to FIGS. 2 or 9. [Measurements of fusing point, thermolysistemperature and spectrum]Fusing point and thermolysis temperature weremeasured in the nitrogen stream at a temperature-raising speed=10°C./min., by performing thermogravimetry and differential thermalanalysis using a device for simultaneous measurement ofthermogravimetry/differential (TG/DTA6000, product of Seiko InstrumentsInc.). According to the results of measurement, the fusing point andthermolysis temperature were found.

₁H-NMR spectrum was measured using JMN A-400 (product of JEOL: 400MHz)with a solvent of CDCl₃. Similarly, ¹³C-NMR spectrum was measured usingJMN A-400 (product of NIHON DENSI: 400 MHz) with a solvent of CDCl₃.

Ultraviolet absorption spectrum was measured using an ultravioletvisible spectrophotometer (V-550, product of JASCO) with a solvent ofacetonitrile.

Infrared absorption spectrum was measured using a Herschel FT-IR-430(JACSO).

Profiling of powder X-ray diffraction spectrum was carried out usingRINT-2100 (RIGAKU) with monochromic CuL_(a) irradiation (λ=1.5418 Å).

[X-ray crystal structure analysis]

X-ray crystal structure analysis was performed by a Mo—Kα irradiation(1=0.71073 Å) monochromated by graphite, using a R-AXIS RAPID ImagingPlate diffractometer. The structure was analyzed by a direct methodusing SIR92 program, and was determined by a least-squares method. Allcalculations here were performed with crystal analysis software “CrystalStructure” (Molecular Structure Corporation).

EXAMPLE 1

(Z, Z)—muconic acid di(4-methoxy benzyl) and (E, Z)—muconic aciddi(4-methoxy benzyl) were obtained as follows.

2.08 g (14.5 mmoL) (Z, Z)—muconic acid (product of Mitsubishi Chemical)and 20 ml hexamethylphospholamide (product of Tokyo Kasei) were mixed ina 100 mL eggplant-shaped flask; then a calcium chloride tube is attachedto the eggplant-shaped flask, and the liquid was stirred until the (Z,Z)—muconic acid dissolved, thus creating a hexamethylphospholamidesolution. Then, 5.05 g (36.6 mmol) potassium carbonate (product of WakoPure Chemical) and 6.06 g (42.1 mmol) 4-methoxy benzyl chloride wereadded to the solution and the mixture was stirred for three days tocause reaction of the substances, thus obtaining a reaction mixture.

Next, 200 ml water was added to the reaction mixture, followed by twotimes extraction with 100 ml chloroform. The extraction liquid wascleaned by water and saturated salt water. Then, the resulting liquidwas dried by sodium sulfate, and the chloroform was removed under lowpressure, thus obtaining a yellow liquid. Further, methanol and waterwere added to the yellow liquid, and the separated white solid body wasfiltered and the resulting solid was dried under low pressure at a roomtemperature. The dried white solid body was subjected to columnchromatography (Wako Gel C-200, chloroform), and the solvent was takenfrom the first liquid, followed by further drying, thus obtaining 3.02 g(yield=54%) (Z, Z)—muconic acid di(4-methoxy benzyl). Further, 0.71 g(yield=24%) (E, Z)—muconic acid di(4-methoxy benzyl) was obtained fromthe second liquid.

The fusion point and spectrum data of the obtained (Z, Z)—muconic aciddi(4-methoxy benzyl) and (E, Z)—muconic acid di(4-methoxy benzyl) areshown in Tables 1 through 6. TABLE 1 FUSION POINT OF MUCONIC ACID DI(4-METHOXY BENZYL) CONFIGURATION FUSING POINT/° C.(CHCl₃) (Z, Z)FORM82.9-83.2 (E, E)FORM 119.8-121.8 (E, Z)FORM 83.8-84.8

TABLE 2 CHEMICAL SHIFT OF PEAK OF ¹H-NMR SPECTRUM OF MUCONIC ACID DI(4-METHOXY BENZYL) (Z, Z) FORM (E, E) FORM CONFIGURATION CHEMICALCHEMICAL ATTRIBUTION SHIFT SHIFT POSITION OF H NUMBER OF H δ/ppm δ/ppm—CH═CHCO₂R 2H 7.91(m) 7.28-7.34(m) —C₆ H ₄ 4H 7.30-7.35(m) 4H6.88-6.93(m) 6.92-6.88(m) —CH═CHCO₂R 2H 6.00(m) 6.20(m) —CH ₂ 4H 5.13(s)5.14(s) —OCH ₃ 6H 3.82(s) 3.81(s)

TABLE 3 CHEMICAL SHIFT OF PEAK OF ¹³C-NMR SPECTRUM OF MUCONIC ACID DI(4-METHOXY BENZYL) (Z, Z) (E, E) FORM FORM CONFIGURATION CHEMICALCHEMICAL ATTRIBUTION SHIFT SHIFT POSITION OF C δ/ppm δ/ppm —C═O 165.48165.76 —C₆H₄ 159.70 159.77 —CH═ 138.21 141.08 —C₆H₄ 130.18 130.27 127.80128.31 124.11 127.70 —CH═ 114.00 114.00 —CH₂ 66.13 65.56 —OCH₃ 55.3055.30

TABLE 4 ABSORPTION PEAK OF ULTRAVIOLET ABSORPTION SPECTRUM OF MUCONICACID DI (4-METHOXY BENZYL) ABSORPTION MOL MAXIMUM ABSORBANCE WAVELENGTHCOEFFICIENT CONFIGURATION λ_(max)(nm) ε(mol⁻¹dm³cm⁻¹) (Z, Z)FORM 22723000 (E, E)FORM 263 28000 (E, Z)FORM 266 27100

TABLE 5 CHEMICAL SHIFT OF PEAK OF ¹H-NMR SPECTRUM OF MUCONIC ACID DI(4-METHOXY BENZYL) ATTRIBUTION CHEMICAL SPIN COUPLING POSITION NUMBERSHIFT CONSTANT OF H OF H δ/ppm J/Hz trans- 1H 8.43 15.6, 11.6(dd)CH═CHCO₂R —C₆ H ₄ 4H 7.20-7.35 —(m) 4H 6.87-6.91 —(m) cis-CH═CHCO₂R 1H6.62 11.6(t) trans-CH═CHCO₂R 1H 6.11 15.6(d) cis-CH═CHCO₂R 1H 5.9611.6(d) —CH ₂ 2H 5.16 —(s) 2H 5.14 —(s) —OCH ₃ 6H 3.81 —(s)

TABLE 6 CHEMICAL SHIFT OF PEAK OF ¹³C-NMR SPECTRUM OF MUCONIC ACID DI(4-METHOXY BENZYL) ATTRIBUTION CHEMICAL SHIFT POSITION OF C δ/ppm —C═O165.91 165.07 —C₆H₄ 159.67 —CH═ 140.78 138.82 —C₆H₄ 130.28 130.19 128.97127.97 127.75 124.54 —CH═ 114.00 113.96 —CH₂ 66.26 63.34 —OCH₃ 55.30

Note that, in Tables 2 and 5, s, d, t and m indicate spectrum peaks insingle line, double line, triple line and multiple line, respectively.

Further, to confirm the crystal structure, X-ray crystal structureanalysis was carried out. FIGS. 2(a) through 2(c), FIGS. 3(a), 3(b) andFIG. 4 show the results for (Z, Z)—muconic acid di(4-methoxy benzyl).

These results of X-ray crystal structure analysis showed that theresulting product was (Z, Z)—muconic acid di(4-methoxy benzyl) (FIGS.3(a), 3(b)) with the column structure illustrated in FIG. 2(a). Further,as shown in FIG. 4, the distance (expressed as d_(s) in the figure)between barycenters of the stacked molecules was 4.74 Å, and thedistance (expressed as d_(cc) in the figure) between carbons of thestacked molecules was 3.44 Å.

Further, as denoted by the broken line in FIG. 2(b), the distancebetween (i) the hydrogen at the portion of carbon-carbon double bondbetween the molecules in the column direction, and (ii) carbonyl oxygenof the carboxyl group was estimated at 2.60 Å to 2.70 Å (see the valuesin the figure). Therefore, it is assumed that there existsintermolecular CH/O interaction in this site in the column structure.Further, as denoted by the broken line in FIG. 2(c), the distancebetween the methoxy group of methoxy benzyl group and the benzene ringwas estimated at 2.83 Å to 3.06 Å (see the values in the figure).Accordingly, it is assumed that there exists intermolecular CH/πinteraction in this site in the column structure.

In contrast, as denoted by the chain double-dashed line in FIG. 2(b),the distance between each methoxy group of the molecules orthogonallypositioned in the column direction was estimated at 2.60 Å (see thevalues in the figure). Accordingly, it is assumed that there existsintermolecular CH/O interaction in this site between the columnstructures.

EXAMPLE 2

(E, E)—muconic acid di(4-methoxy benzyl) was obtained as follows

3.00 g (21.1 mmoL) (Z, Z)—muconic acid and 30 ml hexamethylphospholamidewere mixed in a 100 mL eggplant-shaped flask; then a calcium chloridetube is attached to the eggplant-shaped flask, and the liquid wasstirred until the (Z, Z)—muconic acid dissolved, thus creating ahexamethylphospholamide solution. Then, 4.38 g (31.7 mmol) potassiumcarbonate and 6.61 g (42.2 mmol) 4-methoxy benzyl chloride were added tothe solution and the mixture was stirred for three days to causereaction of the substances, thus obtaining a reaction mixture.

Next, 300 ml water was added to the reaction mixture, followed by twotimes extraction with 150 ml chloroform. The extraction liquid wascleaned by water and saturated salt water. Then, the resulting liquidwas dried by sodium sulfate, and a spatula of iodine was added theretobefore subjected to ultraviolet irradiation for 6 hours using ahigh-pressure mercury lamp (SHL-100-2, 100 W, Pyrel filter; product ofToshiba). After the irradiation, chloroform was removed under lowpressure, thus obtaining a yellow liquid. Further, methanol and waterwere added to the yellow liquid, and the separated white solid body wasfiltered and the solid was dried under low pressure at a roomtemperature, thus obtaining 5.78 g (yield=72%) (E, E)—muconic aciddi(4-methoxy benzyl).

The fusion point and spectrum data of the obtained (E, E)—muconic aciddi(4-methoxy benzyl) are shown in Tables 1 through 4.

Note that, in Table 2, s and m indicate spectrum peaks in single lineand multiple line, respectively.

Further, to confirm the crystal structure, X-ray crystal structureanalysis was carried out. FIGS. 5(a) through 5(b), and FIG. 6 show theresults for (E, E)—muconic acid di(4-methoxy benzyl). These results ofX-ray crystal structure analysis showed that the resulting product was(E, E)—muconic acid di(4-methoxy benzyl) (FIGS. 5(a), 5(b)) with thecolumn structure. Further, as shown in FIG. 6, the distance (expressedas d_(s) in the figure) between barycenters of the stacked molecules was4.87 Å, and the distance (expressed as d_(cc) in the figure) betweencarbons of the stacked molecules was 3.32 Å.

EXAMPLE 3

The same reaction as that of Example 1 was carried out; however, insteadof 4-methoxybenzylchloride, 4-chrolobenzylbromide, 4-bromobenzylbromide,and 2,3,4,5, 6-pentafluorobenzylbromide were used in the sametheoretical amount.

Table 7 shows the production amount of (Z, Z) form and (E, E) form ofthe obtained product. The reaction time is shown in the table. TABLE 7RATIO REACTION BETWEEN TIME YIELD ISOMERS REACTANT (day) (%) (Z,Z):(E,Z)

2 96 ˜100:0

2 82  99:1

1 89 ˜100:0

3 78  70:30

As shown in Table 7, an esterified product was obtained with a highyield. Further, it can also be seen that a mixture of (Z, Z) form and(E, Z) form was obtained in all of the respective cases usinghalogenides with different benzyl groups. Further, in the product, (Z,Z) form is greater in amount than (E, Z) form in all cases.

COMPARATIVE EXAMPLE

Esterification was carried out with a phase-transition catalyst. Morespecifically, as shown in the formula (6), muconic acid was reacted with4-bromobenzylbromide with different bases and solvents (shown in Table8) in the presence of potassium hydrogen tetra n-butylammonium.

Reaction time, reaction condition, theoretical ratio betweenbase/muconic acid, and ratio between isomers of the product is shown inTable 8. Note that, the respective isomers were determined by H-NMRspectrum measurement. TABLE 8 SOLVENT H₂O/ H₂O/ H₂O/ H₂O/ CH₂Cl₂ C₂H₄Cl₂C₂H₄Cl₂ C₂H₄Cl₂ BASE KOH KOH K₂CO₃ KOH THEORETICAL   4.4   4.4   2.2 2.0RATIO (BASE/ MUCONIC ACID) REACTION REFLUX ROOM ROOM ROOM TEMPERATURETEMPER- TEMPER- TEMPERATURE ATURE ATURE REACTION 1 HOUR 3 DAYS 3 DAYS 3DAYS TIME PRODUCT (%) (Z, Z)FORM 17 25 45 1.2 (E, Z)FORM 40 58 10 11  (E, E)FORM — — — —

As shown in Table 8, (Z, Z) form product and (E, Z) product wereobtained, but no (E, E) product. Further, it can also be seen that theproduction amounts of (Z, Z) form and (E, Z) form depend on the reactioncondition.

As shown in FIGS. 7 and 8, the (Z, Z) form and the (E,Z) form wereobtained in both Example 3 and the present comparative example. However,in Example 3, the products were mostly (Z, Z) forms, while the presentcomparative example did not result in production of a particular isomerwith high yield.

EXAMPLE 4

A polymuconic acid di(4-methoxy benzyl) was obtained from (Z, Z)-muconicacid di(4-methoxy benzyl) and (E, E)—muconic acid di(4-methoxy benzyl)produced in Examples 1 and 2.

Specifically, a 31 mg (0.081 mmol) crystal of (Z, Z)—muconic aciddi(4-methoxy benzyl) was placed in a dish and was irradiated withultraviolet light for 8 hours at a room temperature. A high-pressuremercury lamp was placed at a 10 cm distance from the dish. Then, 50 mlchloroform was added to the obtained solid-body, stirred for an hour,and the not-dissolved part was taken out by filtration, thus obtaining29 mg (yield=93%) white powder of polymuconic acid di(4-methoxy benzyl).This polymuconic acid d (4-methoxy benzyl) is hereinafter referred to asa polymer from (Z, Z) form. The same process as above was performedagain with a 110 mg (0.31 mmol) crystal of (E, E)—muconic aciddi(4-methoxy benzyl) was placed in a dish and was irradiated withultraviolet light for 8 hours at a room temperature. Obtained is 96 mg(yield=81%) white powder of polymuconic acid di(4-methoxy benzyl).

Then the obtained polymer from (Z, Z) form and the polymer from (E, E)form were checked for thermal characteristic, and solubility to asolvent. The fusion point was 205° C. and the kick-off temperature was270° C. These results have proved the superior thermotolerancy of thepolymers.

Further, chloroform, 1,2-dichloroethane, o-dichlobenzene, toluen,dimethylformamide, dimethylsulfoxide, tetrahydrofuran,hexamethylphospholamide, trifluoroacetic acid, polar solvent ofhexafluoro isopropanol, and fluorocarbon solvent. These results haveproved the superior solvent resistance of the polymers.

Further, to compare a disyndiotactic polymer with a isotactic polymer insolvent resistance, a disyndiotactic polymer obtained from (E,E)—muconic acid di(4-methoxy benzyl) and a isotactic polymer obtainedfrom (E, E)—muconic acid di(3-methoxy benzyl) were checked forsolubility to organic solvents or acids. The results are shown in Table9. As can be seen is the table, the isotactic polymer was insoluble toorganic solvents, but soluble to strong sulfuric acid or trifluoroaceticacid. In contrast, the disyndiotactic polymer was insoluble not only toorganic solvents but also to strong sulfuric acid or trifluoroaceticacid. Accordingly, disyndiotactic polymer is superior in solventresistance. TABLE 9 DISYNDIOTACTIC POLYMER OBTAINED POLYMER OBTAINED BY(Z, Z) - muconic BY (Z, Z) - 3 muconic acid di (4-methoxy acid di(4-methoxy SOLVENT benzyl) benzyl) DIMETHYLFORMAMIDE INSOLUBLE INSOLUBLEDIMETHYLSULFOXIDE INSOLUBLE INSOLUBLE HEXAMETHYLPHOSPHOLAMIDE INSOLUBLEINSOLUBLE O-DICHLOROBENZENE INSOLUBLE INSOLUBLE CHLOROFORM INSOLUBLEINSOLUBLE TETRAHYDROFURAN INSOLUBLE INSOLUBLE TRIFLUOROACETIC ACIDINSOLUBLE INSOLUBLE CONCENTRATED INSOLUBLE INSOLUBLE SULFURIC ACID

Further, to check the configuration of the obtained polymer, infraredabsorption spectrum, powder X-ray diffraction spectrum were measured.The results are shown in FIGS. 7 and 8.

Further, for X-ray crystal structure analysis, a monocrystal polymuconicacid di(4-methoxy benzyl) was obtained as follows.

More specifically, the 50 mg monocrystal of (Z, Z)—muconic aciddi(4-methoxy benzyl) was degassed and sealed in Pyrex glass seal pipe,and was irradiated with γ ray (200 kGy) using cobalt 60 at a roomtemperature. Obtained was a polymer monocrystal of (Z, Z)—muconic aciddi(4-methoxy benzyl).

Change in reaction with time was observed by infrared absorptionspectrum measurement and powder X-ray diffraction spectrum measurement,and found that the reaction proceeds quantitatively. Further, one withgood quality was picked from the obtained polymer monocrystals for X-raycrystal structure analysis. The result is shown in FIGS. 9(a) and 9(b).

As shown in FIGS. 7 through 9, the obtained polymer has a significantlyhigh stereoregularity and high crystalline property. Further, it alsoshows that the configuration of polymers at the carbon-carbon doublebond is trans, and that the polymers were formed through topochemicalpolymerization, that was reaction between the crystal layers. Further,it also shows that the stereoregularity of the obtained polymers aredisyndiotactic.

Further, disyndiotactic polymer was also obtained through various methodother than the foregoing method. FIG. 10 shows other polymerizationmethods produced disyndiotactic polymer. TABLE 10 STRUCTURE OF STRUCTUREOF IRRADIATION YIELD MONOMER ESTER SUBSTITUENT POLYMER METHOD (%) (Z,Z)- 4-METHOXYBENZYL DISYNDIOTACTIC ULTRAVIOLET 93 LIGHT (Z, Z)-4-ETHOXYBENZYL DISYNDIOTACTIC ULTRAVIOLET 95 LIGHT (E, E)-4-METHOXYBENZYL DISYNDIOTACTIC ULTRAVIOLET 81 LIGHT (E, E)-4-ETHOXYBENZYL DISYNDIOTACTIC ULTRAVIOLET 63 LIGHT (Z, Z)-4-METHOXYBENZYL DISYNDIOTACTIC γ RAY 100 (Z, Z)- 4-ETHOXYBENZYLDISYNDIOTACTIC γ RAY 100 (E, E)- 4-METHOXYBENZYL DISYNDIOTACTIC γ RAY100 (E, E)- 4-ETHOXYBENZYL DISYNDIOTACTIC γ RAY 100 (E, Z)-4-METHOXYBENZYL DISYNDIOTACTIC γ RAY 96 (E, E)- 3-METHOXYBENZYLDIISOTACTIC ULTRAVIOLET 67 LIGHT (E, E)- 3-METHOXYBENZYL DIISOTACTIC γRAY 100

As shown in Table 10, in polymerization of (Z, Z)—muconic aciddi(4-methoxy benzyl) and (E, E)—muconic acid di(4-methoxy benzyl),disyndiotactic polymer was obtained either by irradiation of ultravioletlight for 8 hours at a room temperature or by irradiation of γ ray (200kGy) at a room temperature.

Further, also in polymerization of (E, Z)—muconic acid di(4-methoxybenzyl), disyndiotactic polymer was obtained through irradiation of γray. Here, powder X-ray diffraction spectrum of the crystals of (E,Z)—muconic acid di(4-methoxy benzyl) and the disyndiotactic polymer(polymer from (E, Z form) were measured (FIG. 10). It has shown that thecrystalline property is kept through the polymerization from monomer topolymer.

Further, disyndiotactic polymer was also obtained through polymerizationof the crystal of (Z, Z) or (E, E)—muconic acid di(4-methoxy benzyl)ester that contains 4-ethoxybenzyl as an ester substituent. Note that,the polymerization here was performed in the same manner as that above,either by irradiation of ultraviolet light for 8 hours at a roomtemperature or by irradiation of γ ray (200 kGy) at a room temperature.

Note that, the polymerization reaction and the structure of polymer maychange depending on the position of the ester substituent. Therefore, asshown in Table 10, the polymerization using (E, E)—muconic aciddi(3-methoxy benzyl) as the ester substituent produced diisotacticpolymer, even though the ester substituent has the same methoxy group.Accordingly, it is preferably that the ester substituent is 4-methoxybenzyl or 4-ethoxy benzyl.

INDUSTRIAL APPLICABILITY

As described, the stereoregular polymer of the present invention isobtained through polymerization of an ester derivant, comprising thestep of: forming a lamination crystal structure using a carboxylic acidhaving a carbon-carbon double bond and a compound having a functionalgroup that can react to a carboxyl group of the carboxylic acid, so thatmolecules in two adjacent molecule planes are antiparallel.

More preferably, the ester derivant is produced by reacting a carboxylicacid having a carbon-carbon double bond with a compound having afunctional group that can react to a carboxyl group of the carboxylicacid, using hexamethylphospholamide as a solvent, in the presence of apotassium carbonate.

With this method, an ester derivant with specific stereoregularity canbe obtained at a higher rate while suppressing isomerization of theproduct. Namely, the foregoing esterification carries out reaction withsecure acquirement of an ester derivant having a specific configurationamong the ester derivants at a high selectivity.

The stereoregular polymer of the present invention can be easilyobtained by polymerizing a crystal of the ester derivant either by lightirradiation or heating.

Since the stereoregular polymer of the present invention has adisyndiotactic structure, it is superior in crystallization, mechanicalcharacteristic, solvent resistance, thermostability. Therefore, thepolymer can be used as a desirable material of an engineering plasticetc.

1. A stereoregular polymer of a disyndiotactic structure withhydrocarbon chain repeating units each having at least one estersubstituent and at least one carbon-carbon double bond.
 2. Thestereoregular polymer as set forth in claim 1, having repeating unitsdenoted by a general formula (1):

where R₁ and R₂ are hydrocarbon groups, each of which may have afunctional group.
 3. An ester derivant having a carbon-carbon doublebond and having a lamination crystal structure wherein molecules in twoadjacent molecule planes are antiparallel.
 4. The ester derivant as setforth in claim 3, denoted by a general formula (2):R₃OOC—CH═CH—CH═CH—COOR₄   (2) where R₃ and R₄ are hydrocarbon groups,each of which may have a functional group.
 5. A production method of anester derivant, comprising the step of: forming a lamination crystalstructure using a carboxylic acid having a carbon-carbon double bond anda compound having a functional group that can react to a carboxyl groupof the carboxylic acid, so that molecules in two adjacent moleculeplanes are antiparallel.
 6. A production method of an ester derivant,comprising the step of: reacting a carboxylic acid having acarbon-carbon double bond with a compound having a functional group thatcan react to a carboxyl group of the carboxylic acid, usinghexamethylphospholamide as a solvent, in the presence of a potassiumcarbonate.
 7. A production method of a stereoregular polymer, comprisingthe step of: polymerizing a crystal of the ester derivant as set forthin claim 34 either by light irradiation or heating.